On Pulse Charging of Lead-Acid Batteries

© Cyril Smith, November 2010

1. Introduction

There are claims that pulse charging of lead-acid batteries from the bemf of certain
magnetic motors is an overunity process, the batteries can be charged while the motor is
doing useful mechanical work and the net energy gained (mechanical work plus stored
energy in the battery) is in excess of that supplied to the motor. The overunity is
usually ascribed to the magnetic motor, but this paper examines the possibility that the
overunity comes from the pulse charging process. If this proves to be the case there is
the potential for developing batteries that contain solid-state self-powered pulse
generators that keep the battery topped up while actually delivering power to a load.

2. Battery Electro-Chemistry

2.1. Discharge Process

The positive electrode is lead-oxide PbO2 and the negative electrode Pb while the
electrolyte is dilute sulphuric acid H2SO4 plus H2O. At the positive electrode the
discharge process is
PbO2 + 3H+ + HSO4- + 2e→PbSO4 + 2H2O. (1)
The process consumes two electrons supplied by the external current flow, three H+ ions
and one HSO4- ion taken from the sulphuric acid, to convert one PbO2 molecule into
one PbSO4 molecule and two water molecules. At the negative electrode the chemical
equation is
Pb + HSO4-→PbSO4 + H+ + 2e (2)
Here one HSO4- ion supplied from the sulphuric acid is consumed to convert one Pb
molecule into one PbSO4 molecule releasing one H+ ion and two electrons that are
passed to the external circuit. These processes are illustrated in figure 1.
HSO4

HSO4
H
PbO2 Pb
2e 2e
(PbSO4) H
(PbSO4)

H
H
H2O

+ve Plate -ve Plate

LOAD
Current
Figure 1. Molecular Discharge Process

Adding the internal ion flow yield the situation as shown in figure 2.

1
 HSO4

H2SO4
HSO4
H
PbSO4
H2SO4 PbSO4
e flow e flow
H Strong flow
H
PbO2 Pb
E Field
H
Strong flow
H
H2O

+ve Plate -ve Plate

LOAD
Current

Figure 2. Continuous Discharge Process

The absorption of a HSO4- ion at the surface of the negative electrode leaves a free H+
ion that, along with the other H+ ion released, gets dragged by the electric field towards
the other plate. There we see those H+ ions being absorbed and converted to water.
The net result is a dilution of the acid as the acid molecules get converted to water.

2.2. Charging Process

Here both the positive and the negative electrode are lead sulphate PbSO4 and the
charging process is simply the reverse of (1) and (2). At the positive plate
PbSO4 + 2H2O→ PbO2 + 3H+ + HSO4- + 2e (3)
and at the negative plate
PbSO4 + H+ + 2e→ Pb + HSO4- (4)
as illustrated in figure 3.
HSO4

H
HSO4
PbSO4 PbSO4
2e 2e
H
(PbO2) (Pb)
H
H
H2O

+ve Plate -ve Plate

+ DC -
Source
Current

Figure 3. Molecular Charge Process

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Adding the ion flow to figure 3 gives the picture shown in figure 4.
HSO4

H2SO4
H
HSO4
PbSO4 Weak flow
PbSO4
e flow e flow
H Strong flow
(PbO2) (Pb)
H2SO4
E Field
H
Strong flow
H
H2O

+ve Plate -ve Plate

+ DC -
Source
Current

Figure 4. Continuous Charge Process

Here we see water molecules absorbed at the positive plate while sulphuric acid is
created at both the positive and negative plates.

3. Discussion

It is clear from the chemical formulae that in the charging process the rate of electrode
“manufacture” (molecules per second) is directly related to the current (electrons per
second). Hence the battery charge is directly proportional to the time integral of the
current. Since that current is associated with the nominal cell voltage Vcell it is clear that
the energy Wstored stored by the charge process is given by
Wstored = Vcell ∫ i.dt (5)
That equation runs in reverse for the discharge yielding the current×time product
available from the stored energy, hence the usual expression in terms of ampere-hours.
If no charging current flows then no stored energy is created, so the possibility of pulse
charging by placing a voltage across the battery while virtually zero current flows
(hence zero power) due to ion inertia is not feasible. In fact it can be shown that current
will flow even though ions have not travelled from plate to plate, see figure 5.

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 HSO4
Ionic wavefront
H2SO4

H
HSO4
PbSO4 PbSO4
e flow H e flow
PbO2 H2SO4 Pb
H
H
H2O

+ve Plate Ionic wavefront -ve Plate

+ Step -
Source
Current

Figure 5. Application of a Step Waveform

This shows a time shortly after the initial step of a step charging waveform. H+ ions
from the positive electrode have not yet reached the opposite side, but because of their
relative low mobility they have travelled a further distance than the HSO4- ions leaving
the negative electrode. During this time current is continually flowing from the
charging circuit to supply the ions in this ionic delay line.

If we are to look for an overunity charging process we need, not volts with zero current
but current with zero volts. That realization leads to the possibility described in the next
section, using the capacitance C of the electrodes and supplying current that obeys
∫ i.dt = C ⋅ V pulse (6)
where Vpulse is the change in voltage across C.

4. A Possible Overunity Charging Scheme

The electrical capacitance C between the electrodes although small is not negligible.
The very design of the electrodes (which maximises electrode area while minimising the
separation) also maximises capacitance, and the liquid dielectric has a high relative
permittivity K (e.g. water has K=80). So the possibility exists to supply a fast rise-time
pulse where the capacitance gets charged during that initial rise, but the time scale is too
short for any chemical reaction to take place. This could be done by transformer
coupling, applying the voltage step in series with the load circuit, as shown in figure 6.

This requires a filter following the transformer as shown so as to prevent the pulses
from reaching the load. Then the voltage pulse of amplitude Vpulse sits on top of the cell
voltage Vcell and during the rise time of the pulse we obtain the current impulse (5) into
the cell. That supplies energy of value
W = 0 ⋅ 5C (V pulse ) 2 (7)

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 Pulse input
Filter

Load
Cell

Figure 6. Pulse Charging Circuit

We then have the situation shown in figure 7 where the charge is on the surface of the
electrodes but no chemical reaction has yet taken place.

+ _
+ _
_
+ _
+ _
+ _
+ _
+ High K dielectric _
e flow PbSO4 + _ PbSO4 e flow
+ _
+ _
+ _
+ _
+ _
+ _
+ _
+ve Plate + -ve Plate

+ Step -
Source
Current

Figure 7. Cell Capacitance Charged

Those surface charges will now allow the slower reactions to take place, converting the
surface charge into ions and also converting the electrode molecules into “charged”
versions. If we terminate the pulse at the point where that conversion is complete, we
can stop the otherwise conventional charging process where the pulse is supplying the
ionic current. Thus the pulse must meet two conditions
(a) rise time faster than the chemical reaction time and
(b) pulse width no greater than that reaction time.

We now have the situation where the input pulse energy is given by (7) while increase
in stored energy of the electrodes is given by (5). From (5) and (6) we obtain for that
increase in stored energy
Wstored = C ⋅ V pulse ⋅ Vcell (8)
which is greater than (7), thus indicating overunity. Taking the ratio of (8) to (7) we
obtain the COP as
V
COP = 2 cell (9)
V pulse
This can be a significant value so it is worth exploring this possibility. However we
should be cognisant of the fact that when the pulse is terminated the reducing voltage

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creates a reverse current thus extracting energy from the cell. The hope is that since this
voltage reduction can occur while the initial electronic charge is being converted into
chemical energy, the inherent change of cell impedance during that conversion will
automatically reduce the voltage so the reverse effect will be minimised.

5. Conclusion

There exists the possibility of overunity charging of the lead-acid battery by having
charging pulses that exhibit a fast rise time and an optimum pulse width. Current flows
into the battery during the voltage rise to charge the inter-electrode capacitance, that
time being too short for any chemical reactions to take place. That value of stored
electronic charge is then converted into chemical energy and the pulse is slowly
terminated during this process. The stored chemical energy appears to be greater than
the electrical energy supplied. It is recommended that this possibility be researched.